JPH03255161A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having persistent antistatic properties and excellent mechanical characteristics by compounding a thermoplastic resin and a specific polyamideimide elastomer. CONSTITUTION:70-99 pts.wt. thermoplastic resin, 30-1 pts.wt. transparent polyamideimide elastomer and, if necessary, 10 pts.wt. or lower (based on 100 pts.wt. the sum of the resin and elastomer) at least one electrolyte selected from the group consisting of org. and inorg. electrolytes are compounded to give the title compsn. The elastomer has a relative viscosity in m-cresol at 30 deg.C of 1.5 or higher and is prepd. by copolymerizing a caprolactam, a arom. tri- or tetracarboxylic acid capable of forming an imide ring or an anhydride thereof, an org. diisocyanate, and a polyoxyalkylene glycol contg. 50wt.% or higher polyoxyethylene glycol having a number-average mol.wt. of 500-4000 in such proportions that the molar amt. of the acid is virtually equal to that of the sum of the diisocyanate and polyoxyalkylene glycol and that the amt. of the polyoxyalkylene glycol accounts for 35-85wt.% of the elastomer.

Description

[Detailed description of the invention]

Industrial Field of Application The present invention provides a novel thermoplastic resin composition with excellent antistatic properties, more specifically, a thermoplastic resin composition containing a thermoplastic resin and a polyamideimide elastomer as basic resin components, and which exhibits continuous antistatic properties. The present invention relates to a thermoplastic resin composition that has the same properties as above and has excellent mechanical properties. Conventional technology Conventionally, thermoplastic resins such as polystyrene resins, polyacrylic resins, polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyester resins, and polyacetal resins are inexpensive and have good mechanical strength. Because they have good mechanical properties such as hardness and rigidity, and moldability, they are widely used in many fields depending on their physical properties and economic value. However, these resins have relatively high surface resistance;
It has the disadvantage of being easily charged with static electricity due to friction, etc. For example, polystyrene resin is used for video cassettes, IC
When used as a material for parts of electronic and electrical devices such as cards, copiers, and televisions, problems may occur due to static electricity, and when used as housing materials for home appliances and OA equipment, static electricity is generated and dust adheres due to the charge. This has the drawback of causing undesirable situations such as staining. Polyacrylic resins, polyethylene, polypropylene, etc. also have the problem of being easily stained when used in lighting equipment, various containers, etc. Furthermore, when polyester and polyamide are used for clothing, sheets, etc., static electricity charged by friction is discharged during attachment and detachment, causing discomfort. Therefore, in these thermoplastic resins, it is desired to develop a material that is imparted with antistatic properties without impairing the desirable properties inherent to the resin. Methods of imparting antistatic properties to these thermoplastic resins include, for example, kneading surfactants into them or coating them on the surface. The agent is easily removed by washing with water or rubbing, making it difficult to impart permanent antistatic properties. In order to improve the impact resistance and antistatic properties of polystyrene resins, various methods have been proposed for adding polyamide elastomers to polystyrene resins (Japanese Patent Laid-Open No. 5919
3959, JP 60-23435, JP 63-95251, JP 63-97653). By the way, such polyamide elastomers include polyether ester amide, which has a hard segment made of polyamide and a soft segment made of polyether, and both segments are linked by an ester bond; polyether amide, which has both segments linked by an amide bond; However, these polyamide elastomers have a drawback of low compatibility with polystyrene resins. In order to improve the compatibility with such polyamide elastomers, it has been proposed to improve the impact resistance by using a vinyl copolymer obtained by copolymerizing a vinyl monomer containing a carboxyl group (Japanese Patent Application Laid-open No. 59-193959), since 40% by weight or more of polyamide elastomer must be used, the rigidity inevitably decreases. I; 5 to 80 parts by weight of polyether ester amide and a vinyl copolymer containing a carboxyl group 95 to 201i
A composition has also been proposed, which improves compatibility and imparts antistatic properties (Japanese Patent Application Laid-Open No. 60-23435), but in order to obtain practical antistatic properties, In this case, the amount of polyether ester amide added is large, and the flexural modulus is insufficient. Furthermore, it has been reported that molded products with antistatic properties and gloss can be obtained by using a composition comprising polyether ester amide, rubber-modified polystyrene resin, and carboxyl group-containing vinyl copolymer (Japanese Patent Application Laid-open No. 6395251), and polyamide elastomer to polystyrene resin from 0.01 to
lOpml: Fine dispersion eliminates delamination and also provides antistatic properties (Japanese Patent Laid-Open No. 63-9765
Publication No. 3) is known. In addition, polyether ester amide, polyether amide, and polyester amide are also being considered as polyamide elastomers to be blended with polystyrene resins. However, the polyether amide used in these products is disadvantageous in terms of cost because its manufacturing method is complicated and uses expensive polyether diamine.
Furthermore, polyester polyamide has low hydrophilicity and is difficult to exhibit antistatic effects. In particular, since polyether ester amide is made from relatively inexpensive polyoxyalkylene glycol,
It is also advantageous in terms of cost, and attempts have been made to use it and improve the bending elastic modulus (Japanese Patent Laid-Open No. 63-952).
However, polyether ester amide does not necessarily have sufficient heat resistance, and even when it is kneaded with polystyrene resin, it becomes difficult to obtain the product if it is exposed to high temperatures for a long time during molding. Physical properties such as mechanical properties and antistatic properties may deteriorate depending on the amount of molding. On the other hand, as a method for imparting permanent antistatic properties to polyacrylic resins, for example, (1) a vinyl copolymer having a polyoxine ethylene chain and a sulfonate, carboxylate or quaternary ammonium salt structure is used. (2) Method of kneading polyether ester amide with acrylic resin (JP-A-55-36237, JP-A-63-63739) Methyl acid-acrylonitrile-butadiene-styrene copolymer (MABS
A method of kneading it into a resin (Japanese Unexamined Patent Publication No. 119256/1983) is known. However, in the method (1) above, the vinyl copolymer to be blended is expensive because it uses a special vinyl copolymer, and polyacrylic resins blended with this are inevitably expensive to manufacture. Above, especially JP-A-55-3
The method described in Japanese Patent No. 6237 has drawbacks such as the amount of vinyl copolymer blended is large and the inherent heat resistance of the polyacrylic resin is unavoidably reduced. On the other hand, (2)
In the method, the refractive index of amorphous polyether ester amide and MBS resin or MABS resin is set to 0.0.
2 or less, the transparency of the resulting composition is maintained, but there is little freedom in combinations, and with polymethyl methacrylate, a typical polyacrylic resin, it is difficult to match the refractive index, and transparency is impaired. There is a drawback. By the way, a major feature of polyacrylic resin is that it has excellent transparency, and when kneading a polymer compound to impart permanent antistatic properties to the polyacrylic resin, the compatibility is poor and the transparency is reduced. It is often damaged. Furthermore, even if a material with good transparency is obtained, a sufficient antistatic effect may not be obtained or the heat resistance may be reduced. Furthermore, if a polymer compound with a complicated structure is manufactured in order to exhibit a sufficient antistatic effect, the manufacturing cost will increase, and it will not be possible to produce a polyacrylic resin having an inexpensive antistatic property. In addition, compositions in which polyamide elastomer is kneaded with polyacecool resin are also known for the purpose of improving antistatic properties and impact resistance (Japanese Patent Application Laid-open Nos. 191752-1982 and 183345-1980). . Polyacetal resin has a strong tendency to decompose at temperatures higher than 200°C, and in the examples of the publication, only 12-nylon polyamide elastomer, which has a melting point equal to or lower than that of polyacetal resin, is used. However, a composition obtained by kneading this 12-nylon polyamide elastomer does not have sufficient antistatic properties. Furthermore, for polyolefin resins, compositions containing polyamide elastomers are known in order to improve dyeability and antistatic properties (Japanese Unexamined Patent Publication No. 58-1208
Publication No. 12). In general, 6-nylon polyamide elastomer is considered to be more preferable than 12-nylon polyamide elastomer in order to impart antistatic properties; When added to resins that require high temperatures, the heat resistance is not necessarily sufficient, and when kneaded with resins having a low melting point, it is difficult to disperse finely, which may reduce the toughness of the resulting composition. Therefore, the reality is that a thermoplastic elastomer that provides a thermoplastic resin composition with excellent mechanical properties and permanent antistatic properties has not been known so far. Problems to be Solved by the Invention Under these circumstances, the present invention aims to provide a thermoplastic resin composition that uses a thermoplastic elastomer and has excellent mechanical properties and permanent antistatic properties. It's a waste of time. Means for Solving the Problems The present inventors developed a thermoplastic elastomer whose main soft segment is a thermoplastic resin and polyoxyethylene glycol in order to develop a thermoplastic resin composition that provides a molded product with excellent physical properties. As a result of intensive research on blending with polyoxyalkylene glycol, which is mainly composed of polyoxyethylene glycol, as a soft segment, caprolactam and at least one trivalent or tetravalent compound such as trimellitic acid or bilomeric acid, etc. A polyamideimide elastomer whose node segment is a polyamideimidecarboxylic acid obtained from an aromatic polycarboxylic acid capable of forming two imide rings and an organic diisocyanate compound has heat resistance, and is made of polystyrene resin, polyolefin It has good compatibility with thermoplastic resins such as polyacrylic resins, polyacrylic resins, and polyacetal resins, and exhibits an excellent antistatic effect with a relatively small amount.
By adjusting the amount of organic diisocyanate compound depending on the proportion and molecular weight of the dosegment, it is possible to change the melting point without impairing heat resistance.In other words, by increasing the amount of organic diisocyanate compound used, the melting point can be lowered. The inventors have discovered that as a result, the compatibility with various thermoplastic resins is improved and the toughness of the thermoplastic resin composition can be greatly improved, and the present invention has been completed based on this knowledge. In other words, the present invention comprises (A) a thermoplastic resin, and (B)
(a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring or an acid anhydride thereof, (c) an organic diisocyanate compound, and (d) a number average molecular weight of 500. -4000 polyoxyalkylene glycol containing at least 50% by weight of polyoxyethylene glycol, the amount of component (b) is substantially equimolar to the total amount of components (c) and (d), and (d) ) The amount of the component is 35 to 8 relative to the elastomer.
Polymerized at a rate of 5% by weight, at a temperature of 30%.
A transparent polyamideimide elastomer having a relative viscosity of 1.5 or more in metacresol at a weight ratio of 70:
Contained in a ratio of 30 to 99:1, and optionally at least 10 parts by weight selected from organic electrolytes and inorganic electrolytes per 100 parts by weight of the total amount of component (CXA) and component (B). The object of the present invention is to provide a thermoplastic resin composition containing one of the following. The present invention will be explained in detail below. Examples of the thermoplastic resin as component (A) in the composition of the present invention include polystyrene resin, polyacrylic resin,
Polyolefin resins such as polyethylene and polypropylene, polyacetal resins, polyphenylene ether resins, polycarbonate resins, polyamide resins,
Examples include polyester resins and blends thereof. Examples of the polystyrene resin include rubber-reinforced polystyrene resin, styrene-butadiene-acrylonitrile copolymer (ABS resin), and styrene-rubber copolymer.
Methyl (meth)acrylate (MBS resin), styrene-
Random, pro-quench, or graft polymers that are mainly composed of acrylonitrile copolymer (AS resin) and styrene monomer, and copolymerized with other vinyl monomers such as methyl methacrylate, methyl acrylate, maleimide, acrylamide, etc. can be mentioned. I: Polyblends of rubber-reinforced polystyrene resin and styrene-butadiene copolymer or hydrogenated styrene-butadiene copolymer, polyblends of ABS resin and polycarbonate resin, polyblends of ABS resin and acrylic resin. , polystyrene-based resin mixed with other thermoplastic resins, such as a polyblend of ABS resin and vinyl chloride resin. The rubber-reinforced polystyrene resin is industrially produced by dissolving a rubbery substance in a styrene monomer and subjecting it to bulk or bulk suspension polymerization. As the rubbery substance, polybutadiene, styrene-butadiene copolymer, etc. are used, and the rubbery substance is usually dispersed in the form of particles in a styrene resin with an average particle size of 0.5 to 5 μm. Furthermore, some of the styrene units constituting these polystyrene resins are σ-methylstyrene units, p-methylstyrene units, p-

[-Also includes those substituted with butylstyrene units, etc. Furthermore, in order to improve the affinity with the polyamideimide elastomer, polystyrene resins containing carboxyl groups, epoquine groups, oxazoline groups, amide groups, hydroxyl groups, amino groups, etc. can also be preferably used. There are no particular restrictions on the method of introducing these functional groups into the polystyrene resin, but acrylic acid, methacrylic acid, fumaric acid, maleic acid, 2-hydroxyethyl methacrylate, 2-hydrocarbon, etc. Quinethyl acrylate, 3-hydroxypropyl methacrylate, maleic anhydride, itaconic anhydride, chloromaleic anhydride, 2-isopropylaminoethylstyrene, aminoethyl acrylate, aminopropyl methacrylate, vinyloxazoline, glycidyl methacrylate, glycidyl acrylate, etc. A monomer having a functional group is added during the polymerization of the polystyrene resin to perform copolymerization. Alternatively, it can also be obtained by mixing a copolymer of these heptamers and styrene with the above-mentioned polystyrene resin. It is not necessarily clear what mechanism produces the antistatic effect when polyamideimide elastomer is kneaded with such functional group-containing polystyrene resin, but it is not clear that the antistatic effect is achieved completely without delamination. It was found that the two had a moderate degree of compatibility, and exhibited excellent antistatic effects and mechanical properties. The content of functional groups in the functional group-containing polystyrene resin is preferably selected from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight. If this content is less than 0.05% by weight, the effect of improving mechanical properties by introducing a functional group will not be sufficiently exhibited, and if it exceeds 10% by weight, the antistatic effect will decrease, which is not preferable. When the functional group is a carboxyl group, the compatibilizing effect is particularly strong, and the amount of carboxyl groups in polystyrene resin is 0.05.
-4% by weight is preferred, more preferably 0.1-2% by weight. When the amount of carboxyl groups is less than 0.05% by weight, the affinity with elastomers containing a large amount of polyamideimide, especially elastomers containing 60% by weight or more of polyamideimide, decreases, resulting in a decrease in impact strength and elongation. When the amount exceeds 4% by weight, the affinity with the polyamideimide elastomer increases, and the elastomer becomes extremely finely dispersed and almost completely compatible. ), so it is not desirable. Examples of the polyacrylic resin include polymethyl methacrylate (MMA resin), rubber-reinforced polymethyl methacrylate, methyl methacrylate-butadiene-styrene copolymer (MBS resin), and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Examples include polymers (MABS resins) and polymers obtained by copolymerizing 60% by weight or more of methyl methacrylate with 40% by weight or less of other copolymers, vinyl heptamers. ,
You may use two or more types in combination. Examples of the copolymerizable vinyl monomers include ethyl methacrylate, butyl methacrylate, methacrylic acid/clohegyfur, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, and diacrylic acid.
-Ethylhexyl, styrene, a-methylstyrene, acrylonitrile, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid and the like. Examples of the polyolefin resin include polyethylene, hollybrobylene, ethylene-propylene copolymer, and polymers obtained by copolymerizing these with other vinyl monomers, and examples of the polyacetal resin include oxymethylene homopolymer and ethylene-propylene copolymer. Oxymethylene copolymers containing oxyalkylene units which differ from oxymethylene units and have 2 to 8 adjacent carbon atoms in the main chain are used. Examples of the polyamide resin include polycondensates of dicarboxylic acids and diamines, 11 condensates of aminocarboxylic acids,
Examples include ring-opening polymers of cyclic lactams, specifically 6-nylon, 4,6-nylon, 6,6-nylon,
Aliphatic polyamides such as 6-IO-nylon, 11-nylon, and 12-nylon, poly(hexamethylene tele7)
Examples include aliphatic-aromatic polyamides such as poly(hexamethylene isophthalamide), poly(tetramethylene isophthalamide), and copolymers and mixtures thereof. Examples of the polyester resin include polyethylene terephthalate, polyethylene terephthalate-polyethylene isophthalate copolymer, polybutylene terephthalate,
A polycondensate of aliphatic glycol-aromatic dicarboxylic acid such as polybutylene teretalate-bolybutylene isophthalate copolymer, a part of the aromatic dicarboxylic acid of the polycondensate is added to an aliphatic acid such as adipic acid, cepatic acid, etc. Examples include those substituted with dicarboxylic acid. Examples of the polycarbonate resin include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ethane, 2.2-bis(4-hydroxyphenyl)propane, and 2.2-bis(4-hydroxyphenyl)propane.
, 5-dichlorophenyl alkanes, etc., and phosgene or diphenyl carbonate, and may be used as a blend of the polycarbonate resin and other thermoplastic resins, if necessary. Further, as the polyphenylene ether resin, for example, - formula (R1 and R2 in the formula are each a hydrogen atom, a halogen atom, or a monovalent residue such as an alkyl group or an aryl group having 1 to 4 carbon atoms) A homopolymer obtained from repeating units represented by, or the above repeating units and the general formula (wherein R'', R''R1 and R6 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, respectively) A monovalent residue such as a group, and R5 and R6 cannot be both hydrogen atoms at the same time. Typical examples of polyphenylene ether homopolymers include:
Poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2,6-danityl-1,4-phenylene) ether, poly (2-ethyl-6-〇-propyl-1,4-7enylene)ether, poly(2,6-di-n-propyl-1,4-7enylene)ether, poly(2-methyl-6-n-butyl) -1,4-phenylene)
Ether, poly(2-ethyl-6-itubrobyl-1.
4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-7 enylene) ether, poly(2-methyl- 6-chloroethyl = 1.4-
(phenylene) ether, etc. Examples of polyphenylene ether copolymers include alkyl-substituted 2,3,6-drimethylphenol represented by the formula (R', R', R' and R6 have the same meanings as above) Examples include polyphenylene ether copolymers that are mainly composed of a polyphenylene ether structure obtained by copolymerizing phenol and a monoalkylphenol such as cresol. These polyphenylene ether resins may be used as a blend with polystyrene resin. In the composition of the present invention, one type of thermoplastic resin for the IR portion (A) may be used, or two or more types may be used in combination. In the composition of the present invention, the polyamide-imide elastomer used as component (B) is composed of (a) caprolactam, (b) trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, or these acids. anhydride, (C) an organic diisocyanate compound, and (d) a polyoxyalkylene glycol containing at least 50% by weight of a polyoxyethylene glycol having a number average molecular weight of 500 to 4000.
A multi-block type copolymer in which polyamideimide, which is a hard segment obtained from components a), component (b), and (c) ff, and glycol, which is a component (d), which is a soft segment, are linked by ester bonds. It is a combination. The trivalent aromatic polycarboxylic acid used as the component (b), that is, the aromatic tricarboxylic acid, specifically includes 1.2.4-trimellitic acid, 1.2.5-
naphthalene tricarboxylic acid, 2.6.7-naphthalene tricarboxylic a, 3.3', 4-diphenyltricarboxylic acid, benzophenone-3,3', 4-1-! J carboxylic acid, diphenylsulfone-3,3', 4-tricarboxylic acid, diphenyl ether-3,3', 4-tricarboxylic acid, and the like. In addition, examples of tetravalent aromatic polycarboxylic acids, that is, aromatic tetracarboxylic acids include pyromellitic acid,
diphenyl-2,2',3,3'-tetracarboxylic acid,
Benzophenone-2,2', 3.3'-tetracarboxylic acid, diphenylsulfone-2,2', 3.3'-tetracarboxylic acid, diphenyl ether-2,2', 3.3'
-tetracarboxylic acids and the like. The aromatic polycarboxylic acid or its acid anhydride as component (b) may be used alone or in combination of two or more, and (c) the organic diisocyanate compound of J& and (d) It is used in a substantially equimolar amount, that is, 0.9 to 1.1 times the mole of the total amount of the component glycol. Examples of the organic diisocyanate compound used as the ff component (c) include hexamethylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, inphorone diisocyanate, diphenylmethane diisocyanate, and the like. One type of these diisocyanate compounds may be used, or two or more types may be used in combination. By using these organic diisocyanate compounds, a heterogeneous structure is introduced into the hard segment, making it possible to lower the melting point and crystallization temperature of the hard segment, making it easier to finely disperse it when kneading with thermoplastic resin. It becomes possible to control the fluidity of the molding process. Furthermore, the introduction of the imide ring increases the thermal decomposition temperature and improves thermal stability during kneading. It is desirable that the amount of the organic diisocyanate compound used as component (c) is equal to or less than equimolar to the glycol component (d); if it is used in an amount larger than this, the melting point may become too low, although it depends on the composition. This is undesirable because the mechanical properties of the composition deteriorate. Polyamide-imide, which is a hard segment, is involved in the heat resistance, strength, hardness, and compatibility of the elastomer with the thermoplastic resin, and the polyamide-imide content in this elastomer must be in the range of 15 to 65% by weight. is necessary. If this content is less than 15% by weight, the strength of the elastomer will be low, and when kneaded into a thermoplastic resin,
It is not preferable because the impact strength becomes low, and 65Ii amount%
Exceeding this is not preferable because the compatibility with the thermoplastic resin becomes poor and the antistatic effect becomes low. Particularly in the case of polyacrylic resin, the influence of the hard segment content is large; for example, in order to maintain transparency when kneaded with MMA resin, the hard segment content must be 40
It is preferable that it is less than % by weight. Further, the number average molecular weight of the polyamideimide is preferably 500 to 3000, more preferably 500 to 2000.
It is desirable that it be within the range of . This number average molecular weight is 500
If it is less than 3,000, the melting point may be low and the heat resistance may be insufficient, and if it exceeds 3,000, the elastomer tends to be less compatible with the thermoplastic resin, which is not preferable. In the composition of the present invention, a polyoxyalkylene glycol containing 50% by weight or more of polyoxyethylene glycol is used as the component (d) in the polyamideimide elastomer, but from the viewpoint of antistatic properties,
Preference is given to using polyoxyethylene glycol alone. The number average molecular weight of the polyoxyethylene glycol used must be in the range of 500 to 4,000. If it is less than 500, it depends on the composition of the elastomer,
It is not preferable because the melting point may become low and the heat resistance may become insufficient. Moreover, if it exceeds 4000, it becomes difficult to form a tough elastomer, and when kneaded into a thermoplastic resin, a decrease in impact strength and rigidity may occur, which is not preferable. Polyoquine alkylene glycol that can be used in combination with polyoxyethylene glycol is less than 50% by weight of the glycol component and has a number average molecular weight of 500 to 40.
00 polyoxinetetramethylene glycol, modified polyoxytetramethylene glycol, polyoxypropylene glycol, etc. can be used. The modified polyoxytetramethylene glycol is -(CH2
) Part of 1-0- -1? Examples include those replaced with -0-. Here, R is an alkylene group having 2 to IO carbon atoms, such as an ethylene group, a 1,2-propylene group,
Examples include 1,3-propylene group, 2-methyl-1,3-propylene group, 2,2-dimethyl-1,3-propylene group, pentamethylene group, and hexamethylene group. There is no particular restriction on the amount of modification, but it is usually 3 to 50% by weight.
selected within the range. The amount of modification and the type of alkylene group are appropriately selected depending on the required properties of the thermoplastic resin composition, such as low-temperature impact resistance and heat resistance. This modified polyoxytetramethylene glycol can be produced, for example, by copolymerization of tetrahydro-7rane and diol using a heteropolyacid as a catalyst, or by copolymerization of diol or a cyclic ether that is a condensation product of diol and butanediol. can. The polyamideimide elastomer used in the composition of the present invention is preferably homogeneously polymerized, and the homogeneity of this elastomer can be judged by its transparency. Regarding the manufacturing method of the polyamideimide elastomer,
Any method that can produce a homogeneous amide-imide elastomer may be used; for example, the following method may be used. That is, (a) caprolactam, (b) aromatic polycarboxylic acid component, (C) organic diincyanate compound component, and (d) glycol component are combined in an amount of (c)
The water content in the resulting polymer is 0.1 to 0.1 when mixed in a proportion that is substantially equimolar to the total amount of the components and (d) fR, min.
This is a method of polymerizing at 150 to 300°C, more preferably 180 to 280°C, while maintaining the content at 1% by weight. In this method, the reaction temperature can also be raised stepwise during dehydration condensation. At this time, some caprolactam remains unreacted, but this is distilled off under reduced pressure and removed from the reaction mixture. The reaction mixture after removing unreacted caprolactam can be further polymerized by post-polymerization under reduced pressure at 200 to 300"C, more preferably at 230 to 280"C, if necessary. In this reaction method, By simultaneously causing esterification and amidation during the dehydration condensation process, coarse phase separation is prevented and a homogeneous and transparent elastomer is produced.This has excellent compatibility with thermoplastic resins and When kneaded with resin, it exhibits excellent antistatic effects and mechanical properties, and unlike polyacrylic resins, it can provide a transparent composition. Simultaneous esterification reaction and caprolactam polymerization by controlling the rate of each reaction,
In order to obtain a transparent and homogeneous elastomer, it is necessary to remove the generated water from the system and maintain the water content in the reaction system in the range of 0.1-1% by weight during polymerization. is preferred. When this water content exceeds 1% by weight, the heavy metal of caprolactam takes priority and coarse phase separation occurs;
If the amount is less than % by weight, esterification takes priority and caprolactam does not react, making it impossible to obtain an elastomer with the desired composition. This water content is appropriately selected within the above range depending on the desired physical properties of the elastomer. Furthermore, in this reaction, the water content in the reaction system may be gradually reduced as the reaction progresses, if desired. This moisture content can be controlled by, for example, reaction temperature,
This can be done by controlling reaction conditions such as the flow rate of inert gas introduced and the degree of pressure reduction, or by changing the reactor structure. The degree of polymerization of the polyamideimide elastomer used in the composition of the present invention can be changed as desired, but
It is necessary to adjust the relative viscosity, measured at 30° C. at 0.5% (weight/volume) in meta-cresol, to be 1.5 or higher. If it is lower than 1.5, the mechanical properties cannot be sufficiently exhibited, and even when kneaded into a thermoplastic resin, the mechanical properties may be insufficient. A preferable relative viscosity is 1.6 or more. Another polymerization method is a method in which (b) an aromatic polycarboxylic acid component and (c) an organic diisocyanate compound component are first reacted, and then (a) caprolactam and (d) a glycol component are reacted together. , or (a
) A portion of caprolactam, (b) an aromatic polycarboxylic acid component, and (C) an organic diisocyanate compound component are reacted, and then (a) caprolactam and (
d) A method can also be used in which a glycol component is added together and reacted. If polymerized using these methods,
Phase separation during polymerization can be prevented and a transparent elastomer can be obtained. When producing a polyamideimide elastomer, an esterification catalyst can be used as a polymerization accelerator. Examples of the polymerization accelerator include phosphoric acid, polyphosphoric acid,
Phosphorous compounds such as metaphosphoric acid: Tetraalkylorthotitanates such as tetrabutyl orthotitanate: Tetraalkoxyzirconiums such as tetrabutylzirconium; Tin-based catalysts such as dibutyltin oxide and dibutyltin laurate; Manganese-based catalysts such as manganese acetate;
Antimony-based catalysts such as antimony trioxide; lead-based catalysts such as lead acetate are suitable. The catalyst may be added at the initial stage of polymerization or at the middle stage of polymerization. In addition, in order to increase the thermal stability of the obtained polyamide-imide elastomer, stabilizers such as various heat-resistant anti-aging agents and antioxidants can be used. May be added. It can also be added after polymerization and before kneading the thermoplastic resin. Examples of the heat stabilizer include N,N'-hexamethylene-bis(3,5-di[-butyl-4-hydroquininnamide), 4,4'-bis(2,6-di(-
butylphenol), 2,2'-methylenebis(4-
Various hindered phenols such as ethyl-6-(-butylphenol), N,N'-bis(β-naphthyl)-p-phenylenediamine, N,N'-diphenyl-
Aromatic amines such as p-phenylenediamine and poly(2,2,4-trimethyl-1,2-dihydroquinoline); copper salts such as copper chloride and copper iodide; sulfur such as dilaurylthiodipropionate Examples include compounds and phosphorus compounds. Thermoplastic resin as component (A) and (B) in the composition of the present invention
The ratio of component (B) to the polyamide-imide elastomer must be in the range of 70:30 to 99:1 by weight; if component (B) is less than this, a sufficient antistatic effect cannot be obtained; If it is more than this, the rigidity will be insufficient. In the composition of the present invention, an organic electrolyte or an inorganic electrolyte may be added as component (C) in order to improve antistatic properties. Said (B) ff
By using the 1 minute polyamideimide elastomer and the electrolyte as component (C) together, a composition with better antistatic properties can be obtained due to the synergistic effect. Examples of organic electrolytes that exhibit such effects include organic compounds having acidic groups, metal salts thereof, organic ammonium salts, and organic phosphonium salts. Examples of the organic compound having an acidic group or its metal salt include dodecylbenzenesulfonic acid, p-)luenesulfonic acid, dodecyl diphenyl ether disulfonic acid, naphthalene sulfonic acid, a condensate of naphthalene sulfonic acid and formalin, and polystyrene sulfonic acid. Alkyl sulfonic acids such as aromatic sulfonic acids and lauryl sulfonic acids, organic carboxylic acids such as stearic acid, lauric acid, and polyacrylic acid, organic phosphoric acids such as diphenyl phosphite and diphenyl phosphate, their alkali metal salts, and alkalis. Examples include earth metal salts. Although it is effective even in the form of a free acid, it is preferable to use it in the form of an alkali metal or alkaline earth metal salt.
For example, sodium, lithium, potassium, magnesium, and calcium salts are preferred. Examples of organic ammonium salts include quaternary ammonium salts such as trimethyloctylammonium bromide, trimethyloctylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, and trioctylmethylammonium bromide; examples of organic phosphonium salts include Examples include quaternary phosphonium salts such as amyltriphenylphosphonium bromide and tetrabutylphosphonium bromide. On the other hand, Mua! As electrolytes, periodic table 1a, Ib, 11
Examples include nitrates, hydroxides, halides, rhodan salts, sulfates, phosphates, and carbonates of group metals such as AgN0. , Ca(NOx)z,
KBr, KNC5%KNO,,1iNO3, LiCl
5NaBr, Na, CO,, NafhPOi CLI (
NOx)t, Zn5O,, Zn(NOz)z, MgC
+ ,,Mg(Now)2,MnCl t,N1(NO
Examples include x)z. These electrolytes may be used alone or in combination of two or more, and are appropriately selected depending on the properties of the thermoplastic resin, the composition of the polyamide-imide elastomer, the purpose of use, and the like. Organic sulfonates are particularly suitable for polyacrylic resin compositions that require transparency. In the composition of the present invention, the above-mentioned (
The amount of electrolyte added as component C) is 10 parts by weight or less, preferably 0.01-10 parts by weight, more preferably 0.1 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). ~
The amount is selected within the range of 5 parts by weight. If this amount is less than 0.01 parts by weight, the effect of the additive will not be fully exhibited, and if it exceeds 10 parts by weight, it will cause a decrease in impact strength, the appearance of corrosion mold deposits on the mold, and a deterioration in appearance. do not have. Further, among these electrolytes, organic electrolytes are more preferable than inorganic electrolytes in terms of mold corrosion resistance and appearance. The composition of the present invention may contain various additive components as desired, such as pigments, dyes, reinforcing fillers, heat stabilizers, antioxidants, nucleating agents, lubricants, and plasticizers, to the extent that the objects of the present invention are not impaired. , UV absorbers, mold release agents, flame retardants, other polymers, etc.
It can be contained in any process such as a crosstalk process or a molding process. Examples of reinforcing fillers include fibrous reinforcing agents such as glass fiber, carbon fiber, and potassium titanate, and granular or Among these, glass fibers and mica are particularly preferred. Furthermore, examples of the flame retardant used to impart flame retardancy to the thermoplastic resin composition include organic halogen-based, organic phosphorus-based, and metal hydroxides. The composition of the present invention can be prepared by mixing the mixture consisting of the component (A), the component (B), the component (C) used as necessary, and various additive components using a known method, for example, using a Banbury mixer, mixing roll, shaft or It can be prepared by kneading using a twin-screw extruder or the like. The kneading temperature at this time is preferably in the range of 180 to 280°C. If the electrolyte has a high melting point, it is better to dissolve the electrolyte in a solvent such as water, alcohol, or dimethylformamide in advance, and then drop this solution into the vent of the extruder to distribute the electrolyte evenly. This is advantageous because a composition with good antistatic effect, mechanical properties, appearance, etc. can be obtained. The thermoplastic resin composition thus obtained can be processed by known methods generally used for molding thermoplastic resins, such as injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, film molding, and sheet molding. , foam sheet molding, foam bead molding, and other methods. The molded article obtained from the composition of the present invention thus obtained has a lasting antistatic property, and its shape is not particularly limited. For example, Fine Chemical Report No. “New Trends in Plastic Materials for Electrical and Electronic Equipment” (published September 20, 1986)
(2) It can be molded into equipment parts of any shape as described in Equipment Compilation, pages 14 to 114. Examples of such items include VTR cassette tape cases, halves, reels, reel flanges, windows, etc.
Audio cassette tape halves, cases, windows, etc.
Copy machine top cover, original cover, inner cover,
Front cover, operation surface cover, charging insulator, paper storage box, paper storage box cover, paper guide, copy paper tray, etc.
TV caps, front frames, back covers, escutcheons, carbon blocks, terminal boards, etc.
Phone housings, handset cases, etc., vacuum cleaner main cases, dust cases, storage cases, rotating hoses, extension tube hoses, top lids, filter boxes, etc., electric fan propeller fans, front covers, rear covers, etc., near conditioner Front panel, Flobella fan, Cross 70 fan, airflow control board, terminal cover, filter chassis, control panel, decorative cover, etc., IC package for semiconductor devices, Micro 70 Tsubi,
Examples include cases for discs, cartridges for optical discs, exterior housings for office printers, display panels, paper guides, connectors, platen knobs, printer bodies, cassette covers, cassette guides, etc. Recently, there has been a demand for higher performance of the above-mentioned equipment and its parts, and there is also a strong demand for excellent antistatic properties. The challenge is not only to prevent dust caused by charging, noise and dropouts, but also to prevent the tape from becoming tangled or stopping when running for a long time, such as with cassette tapes for VTRs. Furthermore, these antistatic effects are required to be maintained for a long period of time and not to be lost even when washed with water. At the same time, it must be lightweight and have high mechanical strength, and good appearance as a molded product is also essential. A molded article produced using the composition of the present invention has all of these characteristics, and furthermore, it is possible to reduce costs, and has great industrial significance. Effects of the Invention The mature plastic resin composition of the present invention has a thermoplastic resin and a polyamideimide elastomer as its basic resin components, and has features such as permanent antistatic properties and excellent mechanical properties. However, it is widely used as a molding material that can impart a function of preventing static electricity to various parts, housings, etc. of home appliances such as videos, televisions, cleaners, copying machines, and lighting equipment, as well as office automation equipment. Examples Next, the present invention will be explained in more detail with reference to examples.
The present invention is not limited in any way by these examples. The physical properties of the composition and elastomer were determined according to the following methods. (1) Tensile strength and tensile elongation: Measured at 23° C. and 155% RH using a dumbbell piece having a thickness of 1/8 inch according to ASTM D638. However, since elastomers and nylon resins tend to absorb moisture, the tensile strength and tensile elongation were measured in an absolutely dry state. Further, for the elastomer, a dumbbell piece having a thickness of 1+mm was used. (2) Flexural modulus: Measured at 23° C. and 55% RH using a 1/8 inch thick test piece according to ASTM D790. (3) Izot impact strength: Measured at 23° C. and 55% R) using a 1/8 inch thick notched test piece according to ASTM D256. (4) Charge voltage test: 81 (
An electrostatic voltage was applied at V, and after the voltage was removed, the time required for the charged voltage of the sample to be halved was measured at 23° C. and 155% RH. (5) Relative viscosity of elastomer: Measured in metacresol at 30° C. and 0.5 wt/vo 1%. (6) Thermal decomposition temperature of elastomer: The weight loss temperature was measured using a differential thermal balance at a heating rate of 10° C./min. (7) Haze number of elastomer: Using a sheet with a wall thickness of 1 mm, ASTM D] 003-61
Measurements were made using a haze meter in accordance with 4. (8) Surface resistivity: Using a 1/8 inch thick flat plate, it was measured under the following conditions using a super insulation meter model 5N-10E manufactured by Toa Denpa Kogyo Co., Ltd. (a) After molding, the condition was adjusted for 24 hours at 23° C. and 155% RH, and then measured (initial surface resistivity). (B) After molding, immerse in running water for 10 minutes to remove surface moisture, condition at 23°C and 55% RH for 24 hours, and then measure. (Surface resistivity after washing with water) . (c) After molding, 23°C 155% l? ) Under the conditions of I,
It was measured after being left for 150 days (0 surface resistivity on the 150th day). (9) Cigarette ash adhesion test: Rub the 1/8 inch thick flat plate used for surface resistivity measurement with gauze 100 times, and add 1 liter of cigarette ash to the surface as shown in the figure.
The flat plate 3 was placed on a flat strip (1/4 inch thick) 2 and evaluated according to the following criteria. ◎: No cigarette ash attached ○: A small amount of cigarette ash attached ×: A large amount of cigarette ash attached (to) VTR cassette tape running test: VTR
A 120-minute tape for 5-VH3 is incorporated into the molded body of the cassette half, and actual playback and rewinding are performed continuously using IO.
Driving tests were conducted repeatedly over the course of several days, and evaluations were made according to the following criteria. The above test was conducted using 10 molded bodies made of the same resin composition. ○: When all 10 tapes run well for 10 days. ×: When even one sample stops running halfway through. The test piece for physical property measurement is the injection molding machine using the pellets obtained in Examples and Comparative Examples. 1/8 inch thick flat plate (vertical 90 mm)
Test pieces with a thickness of 1/8 inch and 1/4 inch were used. Further, the thermoplastic resin and electrolyte used in Examples and Comparative Examples are as follows. A-1: Polystyrene resin containing 12% by weight of butadiene rubber A-2: Polystyrene resin (measured at 200'C, 5 kg; melt flow index I: 2.3f?/lo+
++m) A-3: Polystyrene resin copolymerized with 8% by weight of methacrylic acid A-4: ABS resin Stylac ABS^-4130 [
[manufactured by Asahi Kakai Kogyo Co., Ltd.] A-5: AS resin Stylac AS 783 [manufactured by Asahi Kakai Kogyo Co., Ltd.] A-6: Polystyrene resin containing 1% by weight of oxazoline group (manufactured by Dow Chemical Company, XUS- 40056-01) ^-7 Methyl dimethacrylate resin Delvet 8ON [manufactured by Asahi Kasei Kogyo Co., Ltd.] A-8: Boriacetal resin Tenac 3010 (manufactured by Asahi Kasei Kogyo Co., Ltd.) A-9: Boryamide resin A-1030BRT (manufactured by Unitika Co., Ltd.) A-10
+Polybutylene terephthalate resin East PBT 140
1 (manufactured by Toshiku Co., Ltd.) A-11: Polycarbonate resin Taflon A-2700 [manufactured by Idemitsu Petrochemical Co., Ltd.] A-1
2: polyphenylene ether C77Sl)/C-0,
56 (700 form 0.5% solution) of poly(2,6-dimethylphenylene-1,4-ether)] A-13 Nistylon QH405 (manufactured by Asahi Kakai Kogyo Co., Ltd., high impact polystyrene) ^- 14 = Crystalline ethylene-propylene block copolymer [ethylene unit content 9% by weight, MFI (ASTM
D1238) 8.0) C-1 Sodium nidodecylbenzenesulfonate C-2: Potassium bromide C-3: Potassium thiocyanate C-4 = Tetrabutylammonium chloride C-5 Niamyl phenylphosphonium chloride Stirrer, nitrogen introduction In a 500-separable flask equipped with a spout and distillation tube, 97 g of caprolactam, 90 g of polyoxyethylene glyfur with a number average molecular weight of 1490, 16.49 g of trimellitic acid, and 4.5 g of diphenylmethane diisocyanate.
29 (diisocyanate/glycol molar ratio 0.3) was oxidized with N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxycinnamic acid amide) (trade name "Irganox"1098; inhibitor) 0.3g and l=
Preparation, while flowing nitrogen at 5012/min, 150
After melting at 260°C, polymerization was carried out at 260°C for 4 hours. The water content in the reaction solution 1 hour, 2 hours, and 4 hours after the temperature was raised to 260° C. was 0.7, 0.5, and 0.3% by weight, respectively. Next, 10.3 g of tetrabutyl orthochita
was added, the pressure was gradually reduced to 1 Torr, and unreacted caprolactam was distilled out of the system. Further, polymerization was carried out for 2 hours at the same temperature under a pressure of 1 Torr or less to obtain a pale yellow transparent elastomer (B-1) (haze number 45%). The elastomer contains 49% by weight of polyoxyethylene glycol segments, has a relative viscosity of 1.95, and has a tensile strength and elongation of 420 ky/cm" and 750 ky/cm", respectively.
%, and the hardness was 38 in Shore D. Melting points, crystallization temperatures and thermal decomposition temperatures are shown in Table 1. In the same manner as in Production Example 1, an elastomer containing 49% by weight of polyoxyethylene glycol segments with a number average molecular weight of 1490 and a diphenylmethane diisocyanate/polyoxyethylene glycol molar ratio of 0.5 was prepared (
B-2), 0.05 elastomer (B-3) was produced. Its melting point, crystallization temperature and thermal decomposition temperature are shown in Table 1. 1. Caprolactam 61. h, 90 g of polyoxyethylene glycol with a number average molecular weight of 490
, diphenylmethane diisocyano-N, 5 g and trimellitic anhydride 12. A transparent elastomer containing 60% by weight of BoIJ oxyethylene glycol segments was obtained (haze number 42%). This elastomer had a strength of 300 kg/cm', an elongation of 970%, a thermal decomposition initiation temperature of 328°C, and a melting point of 181'C. Production Example 5 Polyamide-imide elastomer (B-5) Kabutuyasudo In a reactor similar to Production Example 1, polyoxyethylene glycol loh with a number average molecular weight of 1980 and caprolactam 4 were added.
5 g, diphenylmethane diisocyanate 1.3 g and trimellitic anhydride 10.7 g were charged together with 0.3 g of poly(2,2,4-trimethyl-1,2-dihydroquinoline) (trade name Tsukrac 224: antioxidant), and nitrogen The reaction was carried out at 250° C. for 4 hours while flowing at a rate of 50 mQ/min. During this period, the water content in the reaction system was 0.8 to 0.3% by weight. Next, the unreacted glolactam was distilled off under reduced pressure at 260"C, the pressure was returned to normal pressure with nitrogen, and 0.3 g of tetrabutoxyzirconium was processed. The pressure was reduced again at 260°C and polymerized at 11 torr for 4 hours, resulting in a pale yellow color. Transparent (
An elastomer with a haze number of 30% was obtained. This elastomer contains 70% by weight of polyoxyethylene glycol segments, has a relative viscosity of 2.11, and a thermal decomposition onset temperature of 325%.
The melting point was 172°C, the strength was 280 kg/ci'', and the elongation was 1100%. Production Example 6 Production of polyamideimide elastomer (B-6) 70 g of polyoxyethylene glycol with a number average molecular weight of 1980, number average molecular weight 2040 polyoxytetramethylene glycol 30°9g, caprolactam 56.39g
Polymerize 13.2 g of pyromellitic anhydride and 1,79 hexamethylene diisocyanate in the same manner as in Production Example 5,
Polyoxyalkylene glycol segment 65% by weight
A pale yellow elastomer containing (haze number 37) was obtained.
%). This elastomer has a relative viscosity of 1.96 and a melting point of 19
1 'C1 pyrolysis start temperature 328°C1 strength 370kg
/cra', and the elongation was 930%. Production Example 7 Production of polyamide-imide elastomer (B-7) 2.23 kg of caprolactam and 2.20 h of polyethylene glycol having a number average molecular weight of 1980 were placed in a 10Q stainless steel reactor equipped with a stirrer, a nitrogen inlet, and a distillation tube.
g, 224 kg of anhydrous trimellit m, 13.9 g of diphenylmethane diisocyanate, and 8 g of N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxycinnamic acid amide) were charged together and heated to 150°C. It was heated and melted. Next, the temperature was raised to 250° C. under a reduced pressure of 300 Torr, and polymerization was carried out for 4 hours. Thereafter, the pressure was gradually reduced to 1 Torr, and 0.64 kg of unreacted caprolactam was distilled out of the system. Additionally, 6g of tetra-n-butquine zirconium
was added and polymerized for 2 hours at 260'C under reduced pressure below 1 Torr. The obtained elastomer is transparent (haze number 38)
%), and the polyethylene glycol segment content is 5
5% by weight, a relative viscosity of 1.9, a melting point of 209°C, a thermal decomposition onset temperature of 327°C, a tensile strength and an elongation of 350 kg/cm" and 850%, respectively, and a hardness of Shore A and D of 9133, respectively. Production Example 8 Production of polyamideimide elastomer (B-8) 70 g of polyoxyethylene glycol having a number average molecular weight of 800, 109 g of caprolactam,
21.9 g of trimellitic anhydride and diphenylmethane diisocyanate)6. h was reacted to produce a polyoxyethylene glycol segment containing Ik 40% by weight, relative viscosity 1.83, haze number 58%, melting point 208°C, thermal decomposition start temperature 329°C, strength 520kg/cm'', elongation 63.
0% elastomer was obtained. Production Example 9 Preparation of polyamide-imide elastomer (B-9) The distillation tube in the apparatus of Production Example 1 was replaced with a reflux condenser, and 167 g of caprolactam, 33.29 adipic acid, and 6 g of water were charged, and the mixture was heated at 260°C. A time reaction was performed to produce a polycapramide with terminal carboxyl groups. This product had a number average molecular weight of 883 as determined by acid value measurement. In the apparatus of Production Example 1, 40 g of the polyamide, 96 g of polyoxyethylene glycol (number average molecular weight 2010), and an antioxidant (N,N'-hexamethylene-bis(3,5-
0.3 g of di[-butyl-4-hydroxysilicic acid amide) (trade name, Irganox 1098) and 0.2 g of tetrabutyl orthotitanate were charged, melted at 240°C, and then reduced to 1 torr for 2 hours. , and 1 more
When polymerization was carried out at 260°C for 9 hours, coarse phase separation occurred during the polymerization. This melt became milky white and did not become transparent until the end of polymerization, and the obtained elastomer was pale brown, opaque, and brittle. The thermal decomposition onset temperature of the elastomer is 2
It was 91'O. Example 1-15 Thermoplastic resin, elastomer, and additives were mixed in the proportions shown in Table 3, and kneaded at the temperature shown in Table 2 using a -screw extruder (30 old screw with dullage, L/D = 26). It was extruded and passed through a cooling path to form a bead. After vacuum drying this pellet at 80° C. for 3 hours, injection molding was performed under the conditions shown in Table 2 to prepare a test piece for measuring physical properties. All exhibited excellent gloss. The measured physical property values are shown in Table 3. Table 2 Comparative Examples 1 to 9 According to Examples 1 to 15, the compositions shown in Table 3 were kneaded, extruded, and injection molded, and the physical properties were measured. The results are shown in Table 3. Examples 16 to 18, Comparative Example 1O The acrylic resin compositions shown in Table 4 were prepared by straining in the same manner as in Examples 1 to 15, and the compositions were injection molded and their physical properties were measured. The results are shown in Table 4. In addition, for comparison, comparative compositions shown in Table 4 were prepared,
It was injection molded and its physical properties were measured. The results are also shown in Table 4. Example 19 After washing the test pieces obtained in Examples 1 and 3.9 with water, a charging voltage test was conducted, and the test pieces showed the same antistatic performance as before washing in 3, 3, and 2 seconds, respectively. Also, these should be adjusted to 55% RH.
,After being left at 23℃ for 6 months, a charging voltage test was conducted.
The antistatic performance was 3.4.2 seconds, respectively, and the antistatic performance was unchanged from the initial value. Example 20 The surface gloss of the compositions of Example 15 and Comparative Example 2 was measured by injection molding at 250'O and after remaining in the molder of an injection molding machine at 250°C for 20 minutes. The gloss of Example 15 was 90% and 84%, respectively, with almost no change in gloss. Those of Comparative Example 2 were 73% and 37%, respectively. In addition, the latter caused some rough skin. Examples 21 to 23 Polystyrene resin, elastomer, and electrolyte were mixed in the proportions shown in Table 5, and a twin-screw extruder CAS30 model with a screw diameter of 30 mm, manufactured by Nakatani Kikai Co., Ltd., was used at a cylinder temperature of 230°C and a screw Melt and knead at a rotational speed of 75 rpm, extrude at an extrusion speed of 10Jig/hr,
After forming into three strands, cool with water to about 30°C. The cooled strands were then granulated to obtain pellets of polystyrene resin composition. After drying this pellet in a gear oven at 80°C for about 3 hours, the cylinder temperature was 220°C and the mold temperature was 60°C.
Injection molding was performed under the following conditions to create a test piece for surface resistivity measurement with excellent gloss. Table 5 shows the measurement results of physical properties. In addition, the pellets produced as described above were injection molded to produce molded bodies shown in Table 6 and evaluated. The results are shown in Table 6. In addition, injection molding was carried out in Example 21 with cylinder temperature of 220°C, mold temperature of 60°C, and Example 2.
In Example 2, the cylinder temperature was 240°C, the mold temperature was 45°C, the cylinder temperature was 270°C in Example 23, and the mold temperature was 70°C.
'C! I went there. Comparative Example 11 Polystyrene resin, elastomer, and other additives
They were mixed in the proportions shown in the table, and test pieces and molded bodies shown in Table 6 were prepared in the same manner as in Example 22, and each evaluation was performed. The results are shown in Tables 5 and 6. Example 24 Polyphenylene ether [ηsp/c = 0.56
(0.5 wt% solution of chloroform) poly(2,6-dimethylphenylene-1,4-ether)], Styron. H405 (manufactured by Asahi Kakai Kogyo Co., Ltd., high impact polystyrene), stabilizer (manufactured by Adeka Argus, mark Ao)
-30), polyamideimide elastomer B-4 and electrolyte were mixed in the proportions shown in Table 7, and the screw diameter was 3oI.
After melt-kneading using a II11 twin-screw extruder (AS-30 model, manufactured by Nakatani Kikai Co., Ltd.) at a cylinder temperature of 250'C and a screw rotation speed of 75 rpm, lo#
Extrusion was performed at an extrusion rate of g/hr to form three strands, which were then cooled to about 30°C with water. The cooled strands were then granulated to obtain pellets of a polyphenylene ether resin composition. After drying the conohellet in a gear oven at 80°C for 3 hours, the cylinder temperature was 260” and the mold temperature was 60°.
Injection molding was performed under the conditions of C to create test pieces for measuring physical properties and measuring surface resistivity. All exhibited excellent gloss. Each physical property of these test pieces was evaluated. The results are shown in Table 7. Further, the pellets were injection molded at a cylinder temperature of 260° C. and a mold temperature of 60° C. to produce the laminates shown in Table 8, and the antistatic properties, appearance, and mechanical properties were evaluated. The results are shown in Table 8. Comparative Example 12 Polyphenylene ether, Styron QH405, stabilizer (manufactured by Adeka Argus, Mark AO-30) and electrolyte were mixed in the proportions shown in Table 7, and the test pieces and the ones shown in Table 8 were prepared in the same manner as in Example 24. A stratified body was created and various evaluations were conducted. The results are shown in Tables 7 and 8. Example 25 - Crystalline ethylene-propylene block copolymer [ethylene unit content 911% by weight, MFI (ASTM
D1238) 8.0), polyamideimide elastomers B to 4, and electrolyte were mixed in the proportions shown in Table 9, and a -screw extruder (30 m + * screw with dullage, L/D
-26), kneaded and extruded at 240°C, passed through a cooling bath, and formed into pellets. After drying this pellet at 80° C. for 3 hours in an open gear, injection molding was performed under the following conditions to produce a test piece for measuring physical properties. All exhibited excellent gloss. Cylinder temperature: 230°C Mold temperature: 50'0 Injection pressure Crab 500g/cat Injection time: 15 seconds Cooling time: 15 seconds The measurement results of physical properties are shown in Table 89. was molded into a molded body shown in Table 10,
We conducted an evaluation. The results are shown in Table 1o. Comparative Example 13 A molded product obtained by adding 0.3 to 0.5 parts by weight of a nonionic antistatic agent to 100 parts by weight of the polyolefin resin used in Example 25 had cloudiness on the surface of the molded product. Also, 0
．． In the molded product to which 5 parts by weight was added, whitening and stickiness on the surface of the molded product were observed over time. For those to which 0.5 parts by weight of nonionic antistatic agent was added, test pieces and molded bodies shown in Table 9 were prepared in the same manner as in Example 25, and various evaluations were performed. The result is the 9th
It is shown in Table and Table 10. Example 26.27 A polyamideimide elastomer and an acrylic resin having the types and amounts shown in Table 11 were mixed, and an electrolyte and a hindered amine light stabilizer (2,2,6,6-tetramethyl-4- piperidyl) sebacate, trade name Sanol LS
770, manufactured by Sankyo Co., Ltd.], benzotriazole ultraviolet absorber (2-(5-methyl-2-hydroxyphenyl)
Benzotriazole, trade name Tinuvin P, manufactured by Ciba Geigy) was blended in the amount shown in Table 1I, then vented 4
01111 - Using an extruder, melt kneading and extrusion were performed at a resin temperature of 250°C to form pellets. Next, molded products shown in Table 12 were produced using an injection molding machine at a cylinder temperature of 250°C and a mold temperature of 60°C, and evaluated. The results are shown in Table 12.

[Brief explanation of drawings]

The figure is an explanatory view showing a method for conducting a tobacco ash adhesion test I on a molded article, in which reference numeral 1 indicates cigarette ash, 2 a strip, and 3 a flat plate for testing.

Claims (1)

[Scope of Claims] 1 (A) a thermoplastic resin, and (B) (a) caprolactam, (b) a trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring, or these acids. (c) an organic diisocyanate compound; and (d) a polyoxyalkylene glycol containing at least 50% by weight of a polyoxyethylene glycol having a number average molecular weight of 500 to 4000;
substantially equimolar to the total amount of component and component (d), and (
d) The amount of component is 35-85% by weight based on the elastomer.
A transparent polyamideimide elastomer having a relative viscosity of 1.5 or more in metacresol at a temperature of 30° C., which is polymerized in a weight ratio of 70:30 to 99:1,
Furthermore, in some cases, (C) a heat source containing at least one selected from organic electrolytes and inorganic electrolytes in an amount of 10 parts by weight or less per 100 parts by weight of the total amount of components (A) and (B); Plastic resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from polystyrene resins, polyacrylic resins, polyolefin resins, and copolymer resins thereof. 3. The thermoplastic resin composition according to claim 2, wherein the polystyrene resin has at least one functional group selected from a carboxyl group, an oxazoline group, an epoxy group, a hydroxyl group, an amino group, and an amide group. 4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from polyamide resins, polyester resins, polyphenylene ether resins, polyacetal resins, and polycarbonate resins.